Fumaric Acid/Diol Polyesters and Their Manufacture and Use

Abstract

We disclose a composition containing a polyester comprising about 1 mole part diol units and from about 0.98 mole parts fumaric acid units to about 1.01 mole parts fumaric acid units. In one embodiment, the diol units are 1,3-propanediol units or 1,2-propanediol units. In one embodiment, the polyester is blended with polylactide. In another embodiment, the composition is in a form selected from the group consisting of a plate, a tray, a bowl, a cup, a bowl lid, a cup lid, a fork, a spoon, a knife, a jewel case, and a packaging article. We also disclose a method of manufacturing the composition. The method includes combining about 1 mole part diol, from about 0.98 mole parts fumaric acid to about 1.01 mole parts fumaric acid, and from about 0.0002 mole parts to about 0.0020 mole parts of a polyesterfication catalyst, to yield a combination of diol and fumaric acid; maintaining the combination of diol and fumaric acid under an inert atmosphere at a temperature from about 130° C. to about 190° C. for at least about 2 hr, to yield a molten combination; maintaining the molten combination under vacuum at a temperature from about 130° C. to about 190° C. for at least about 6 hr, to yield a molten polyester; and cooling the molten polyester, to yield the polyester.

1 . A composition, comprising:
 a polyester comprising about 1 mole part diol units and from about 0.98 mole parts fumaric acid units to about 1.01 mole parts fumaric acid units.   
     
     
         2 . The composition of  claim 1 , wherein the diol units are selected from the group consisting of ethylene glycol units, 1,4-butanediol units, 1,2-propanediol units, isosorbide units, and 1,3-propanediol units. 
     
     
         3 . The composition of  claim 2 , wherein the polyester has a melt flow index (MFI) when analysis is performed at 145° C. of less than about 5 g/10 min. 
     
     
         4 . The composition of  claim 1 , wherein the polyester is present at from about 5 weight parts to about 90 weight parts, and the composition further comprises at least one component selected from the group consisting of from about 0.1 weight parts to about 20 weight parts of a plasticizer, from about 0.1 weight parts to about 1 weight part of a pigment, and from about 0.002 weight parts to about 1 weight part of an antioxidant. 
     
     
         5 . The composition of  claim 4 , wherein the plasticizer is a polyethylene glycol or the antioxidant is α-tocopherol. 
     
     
         6 . The composition of  claim 1 , wherein the polyester is present at from about 5 weight parts to about 90 weight parts, and the composition further comprises from about 10 weight parts to about 95 weight parts of a second polymer selected from the group consisting of starch, polylactic acid, and polylactide. 
     
     
         7 . The composition of  claim 6 , wherein the polyester is present at about 50 weight parts and the second polymer is polylactide and is present at about 50 weight parts. 
     
     
         8 . The composition of  claim 1 , wherein the diol units and the fumaric acid units are derived from biomass. 
     
     
         9 . The composition of  claim 1 , in a form selected from the group consisting of a plate, a tray, a bowl, a cup, a bowl lid, a cup lid, a fork, a spoon, a knife, a jewel case, and a packaging article. 
     
     
         10 . A packaging article, comprising:
 a composition comprising a polyester comprising about 1 mole part diol units and from about 0.98 mole parts fumaric acid units to about 1.01 mole parts fumaric acid units.   
     
     
         11 . The packaging article of  claim 10 , wherein the diol units are selected from the group consisting of ethylene glycol units, 1,4-butanediol units, 1,2-propanediol units, isosorbide units, and 1,3-propanediol units. 
     
     
         12 . The packaging article of  claim 11 , wherein the polyester has a melt flow index (MFI) when analysis is performed at 145° C. of less than about 5 g/10 min. 
     
     
         13 . The packaging article of  claim 10 , wherein the polyester is present at from about 5 weight parts to about 95 weight parts, and the composition further comprises at least one component selected from the group consisting of from about 0.1 weight parts to about 20 weight parts of a plasticizer, from about 0.1 weight parts to about 1 weight part of a pigment, and from about 0.002 weight parts to about 1 weight part of an antioxidant. 
     
     
         14 . The packaging article of  claim 13 , wherein the polyester is present at from about 5 weight parts to about 90 weight parts, and the composition further comprises from about 10 weight parts to about 95 weight parts of a second polymer selected from the group consisting of starch, polylactic acid, and polylactide. 
     
     
         15 . The packaging article of  claim 14 , wherein the polyester is present at about 50 weight parts and the second polymer is polylactide and is present at about 50 weight parts. 
     
     
         16 . The packaging article of  claim 10 , wherein the packaging article is selected from the group consisting of a plate, a tray, a bowl, a cup, a bowl lid, a cup lid, a fork, a spoon, a knife, a jewel case, and a packaging article. 
     
     
         17 . A method of manufacturing a composition comprising a polyester comprising about 1 mole part diol units and from about 0.98 mole parts fumaric acid units to about 1.01 mole parts fumaric acid units, the method comprising:
 combining about 1 mole part diol, from about 0.98 mole parts fumaric acid to about 1.01 mole parts fumaric acid, and from about 0.0002 mole parts to about 0.0020 mole parts of a polyesterfication catalyst, to yield a combination of diol and fumaric acid;   maintaining the combination of diol and fumaric acid under an inert atmosphere at a temperature from about 130° C. to about 190° C. for at least about 2 hr, to yield a molten combination;   maintaining the molten combination under vacuum at a temperature from about 130° C. to about 190° C. for at least about 18 hr, to yield a molten polyester; and   cooling the molten polyester, to yield the polyester.   
     
     
         18 . The method of  claim 17 , wherein the diol is selected from the group consisting of ethylene glycol, 1,4-butanediol, 1,2-propanediol, isosorbide, and 1,3-propanediol. 
     
     
         19 . The method of  claim 17 , wherein the polyesterification catalyst is selected from the group consisting of tin(II) chloride, tin(II) octonate, n-butyl stannoic acid, sulfuric acid, p-toluene sulfonic acid, and mixtures thereof. 
     
     
         20 . The method of  claim 17 , further comprising extruding the polyester, to yield a sheet of the composition. 
     
     
         21 . The method of  claim 20 , wherein the extruding step further comprises coextruding with the polyester a second polymer selected from the group consisting of starch, polylactic acid, and polylactide. 
     
     
         22 . The method of  claim 20 , wherein the extruding step further comprises coextruding with the polyester at least one component selected from the group consisting of a plasticizer, a pigment, and an antioxidant. 
     
     
         23 . The method of  claim 20 , further comprising molding the sheet of the composition, wherein the sheet is molded to a form selected from the group consisting of a plate, a tray, a bowl, a cup, a bowl lid, a cup lid, a fork, a spoon, a knife, a jewel case, and a packaging article. 
     
     
         24 . The method of  claim 17 , wherein the diol and the fumaric acid are derived from biomass. 
     
     
         25 . The method of  claim 17 , further comprising reacting the molten polyester with a chain extending agent selected from the group consisting of isocyanates, epoxides, acyl chlorides, anhydrides, acrylics, aziridines, phosphate esters, multivalent metals, polyacids, polyols, oxazolines, polymers or copolymers containing any of the foregoing functional groups, and mixtures thereof. 
     
     
         26 . The method of  claim 25 , wherein the chain extending agent is selected from the group consisting of 4,4′-methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI or HDMI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), trimethylxylene diisocyanate (TMDI or TMXDI), polyisocyanate compounds, and mixtures thereof.